Enhancing Cycling Stability and Capacity Retention of NMC811 Cathodes by Reengineering Interfaces via Electrochemical Fluorination

Thapaliya, Bishnu P.; Misra, Sudhajit; Yang, Shi‐ze; Jafta, Charl J.; Meyer, Harry M.; Bagri, Prashant; Unocic, Raymond R.; Bridges, Craig A.; Dai, Sheng

doi:10.1002/admi.202200035

Title: Enhancing Cycling Stability and Capacity Retention of NMC811 Cathodes by Reengineering Interfaces via Electrochemical Fluorination

Journal Article · 09 February 2022 · Advanced Materials Interfaces

DOI: https://doi.org/10.1002/admi.202200035 · OSTI ID:1873831

^[1];

^[2]; Yang, Shi‐ze ^[3];

^[4];

^[4]; Bagri, Prashant ^[4];

^[2];

^[4];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States). Joint Institute for Advanced Materials
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Arizona State Univ., Tempe, AZ (United States). Eyring Materials Center
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

High-capacity cathodes (LiNi_0.8Mn_0.1Co_0.1O₂) that can boost the energy density of lithium-ion batteries are promising candidates for vehicle electrification. However, several factors specific to high energy density materials entailing electrode reactions inhibit their application. Fluorination has shown a promising ability to combat the detrimental electrochemical performances of cathode materials, however, it remains difficult to achieve the desired functionality. In this work, a novel electrochemical fluorination (ECF) that demonstrates a promising electrochemical performance enhancement via stabilization of the cathode–electrolyte-interphase (CEI) by forming conformal LiF is proposed. Besides LiF surface layer formation, ECF reduces the degree of fluorination-induced Ni/Li disordering and enhances the layered structural stability as probed by X-ray diffraction. Because of the robust CEI, ECF-NMC811 cathodes deliver 203.0 mAh g^-1 first discharge capacity at the current rate of C/10, with ≈98% capacity retention up to 100 cycles. Similarly, it delivers ≈180 mAh g^-1 capacity at a 1 C rate with 86.4% capacity retention up to 200 cycles with average coulombic efficiency of > 99.5%. Comprehensive characterization with a multitude of probes reveals that ECF enhances the cycling stability of the electrode without altering bulk structure and morphology.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725; SC0012704

OSTI ID:: 1873831

Journal Information:: Advanced Materials Interfaces, Journal Name: Advanced Materials Interfaces Journal Issue: 18 Vol. 9; ISSN 2196-7350

Publisher:: Wiley-VCHCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Insight into the Solid Electrolyte Interphase Formation in Bis(fluorosulfonyl)Imide Based Ionic Liquid Electrolytes Jafta, Charl J.; Sun, Xiao‐Guang; Lyu, Hailong Advanced Functional Materials, Vol. 31, Issue 23 https://doi.org/10.1002/adfm.202008708	journal	February 2021
High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes Chen, Shuru; Zheng, Jianming; Mei, Donghai Advanced Materials, Vol. 30, Issue 21 https://doi.org/10.1002/adma.201706102	journal	March 2018
A Novel Electrolyte Salt Additive for Lithium-Ion Batteries with Voltages Greater than 4.7 V Li, Yunchao; Wan, Shun; Veith, Gabriel M. Advanced Energy Materials, Vol. 7, Issue 4 https://doi.org/10.1002/aenm.201601397	journal	November 2016
From Surface ZrO ₂ Coating to Bulk Zr Doping by High Temperature Annealing of Nickel-Rich Lithiated Oxides and Their Enhanced Electrochemical Performance in Lithium Ion Batteries Schipper, Florian; Bouzaglo, Hana; Dixit, Mudit Advanced Energy Materials, Vol. 8, Issue 4 https://doi.org/10.1002/aenm.201701682	journal	September 2017
Prospect and Reality of Ni-Rich Cathode for Commercialization Kim, Junhyeok; Lee, Hyomyung; Cha, Hyungyeon Advanced Energy Materials, Vol. 8, Issue 6 https://doi.org/10.1002/aenm.201702028	journal	November 2017
Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries Liu, Wen; Oh, Pilgun; Liu, Xien Angewandte Chemie International Edition, Vol. 54, Issue 15 https://doi.org/10.1002/anie.201409262	journal	March 2015
Simultaneously Boosting the Ionic Conductivity and Mechanical Strength of Polymer Gel Electrolyte Membranes by Confining Ionic Liquids into Hollow Silica Nanocavities Thapaliya, Bishnu P.; Do‐Thanh, Chi‐Linh; Jafta, Charl J. Batteries & Supercaps, Vol. 2, Issue 12 https://doi.org/10.1002/batt.201900095	journal	September 2019
Fluorination of Li‐Rich Lithium‐Ion‐Battery Cathode Materials by Fluorine Gas: Chemistry, Characterization, and Electrochemical Performance in Half Cells Breddemann, Ulf; Erickson, Evan M.; Davis, Victoria ChemElectroChem, Vol. 6, Issue 13 https://doi.org/10.1002/celc.201900733	journal	July 2019
Fluorination of MXene by Elemental F ₂ as Electrode Material for Lithium‐Ion Batteries Thapaliya, Bishnu P.; Jafta, Charl J.; Lyu, Hailong ChemSusChem, Vol. 12, Issue 7 https://doi.org/10.1002/cssc.201900003	journal	March 2019
Synthesizing High‐Capacity Oxyfluoride Conversion Anodes by Direct Fluorination of Molybdenum Dioxide (MoO ₂ ) Thapaliya, Bishnu P.; Self, Ethan C.; Jafta, Charl J. ChemSusChem, Vol. 13, Issue 15 https://doi.org/10.1002/cssc.202001006	journal	July 2020
An Electron Diffraction and Crystal Chemical Investigation of Oxygen/Fluorine Ordering in Rutile-Type Iron Oxyfluoride, FeOF Brink, Frank J.; Withers, Ray L.; Thompson, John G. Journal of Solid State Chemistry, Vol. 155, Issue 2 https://doi.org/10.1006/jssc.2000.8925	journal	December 2000
Degradation Mechanisms and Mitigation Strategies of Nickel-Rich NMC-Based Lithium-Ion Batteries Li, Tianyu; Yuan, Xiao-Zi; Zhang, Lei Electrochemical Energy Reviews, Vol. 3, Issue 1 https://doi.org/10.1007/s41918-019-00053-3	journal	October 2019
Effects of heteroatoms on electrochemical performance of electrode materials for lithium ion batteries Wu, Y. P.; Rahm, Elke; Holze, Rudolf Electrochimica Acta, Vol. 47, Issue 21, p. 3491-3507 https://doi.org/10.1016/S0013-4686(02)00317-1	journal	August 2002
Highly Fluorinated Interphases Enable High-Voltage Li-Metal Batteries Fan, Xiulin; Chen, Long; Ji, Xiao Chem, Vol. 4, Issue 1 https://doi.org/10.1016/j.chempr.2017.10.017	journal	January 2018
Improving the cycling performance of LiNi0.8Co0.1Mn0.1O2 by surface coating with Li2TiO3 Meng, Kui; Wang, Zhixing; Guo, Huajun Electrochimica Acta, Vol. 211 https://doi.org/10.1016/j.electacta.2016.06.110	journal	September 2016
A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries Manthiram, Arumugam; Song, Bohang; Li, Wangda Energy Storage Materials, Vol. 6 https://doi.org/10.1016/j.ensm.2016.10.007	journal	January 2017
Chemical stability and long-term cell performance of low-cobalt, Ni-Rich cathodes prepared by aqueous processing for high-energy Li-Ion batteries Wood, Marissa; Li, Jianlin; Ruther, Rose E. Energy Storage Materials, Vol. 24 https://doi.org/10.1016/j.ensm.2019.08.020	journal	January 2020
Significantly improving cycling performance of cathodes in lithium ion batteries: The effect of Al2O3 and LiAlO2 coatings on LiNi0.6Co0.2Mn0.2O2 Liu, Wen; Li, Xifei; Xiong, Dongbin Nano Energy, Vol. 44 https://doi.org/10.1016/j.nanoen.2017.11.010	journal	February 2018
Ni/Li Disordering in Layered Transition Metal Oxide: Electrochemical Impact, Origin, and Control Zheng, Jiaxin; Ye, Yaokun; Liu, Tongchao Accounts of Chemical Research, Vol. 52, Issue 8 https://doi.org/10.1021/acs.accounts.9b00033	journal	June 2019
Capacity Fading of Ni-Rich Li[Ni _x Co _y Mn _{1– x – y} ]O ₂ (0.6 ≤ x ≤ 0.95) Cathodes for High-Energy-Density Lithium-Ion Batteries: Bulk or Surface Degradation? Ryu, Hoon-Hee; Park, Kang-Joon; Yoon, Chong S. Chemistry of Materials, Vol. 30, Issue 3 https://doi.org/10.1021/acs.chemmater.7b05269	journal	January 2018
Evolution of Structure and Lithium Dynamics in LiNi _0.8 Mn _0.1 Co _0.1 O ₂ (NMC811) Cathodes during Electrochemical Cycling Märker, Katharina; Reeves, Philip J.; Xu, Chao Chemistry of Materials, Vol. 31, Issue 7 https://doi.org/10.1021/acs.chemmater.9b00140	journal	March 2019
Improving Performance of LiNi _0.8 Co _0.1 Mn _0.1 O ₂ Cathode Materials for Lithium-Ion Batteries by Doping with Molybdenum-Ions: Theoretical and Experimental Studies Susai, Francis Amalraj; Kovacheva, Daniela; Chakraborty, Arup ACS Applied Energy Materials, Vol. 2, Issue 6 https://doi.org/10.1021/acsaem.9b00767	journal	May 2019
Long-Life Nickel-Rich Layered Oxide Cathodes with a Uniform Li ₂ ZrO ₃ Surface Coating for Lithium-Ion Batteries Song, Bohang; Li, Wangda; Oh, Seung-Min ACS Applied Materials & Interfaces, Vol. 9, Issue 11 https://doi.org/10.1021/acsami.7b00070	journal	March 2017
Enhanced Cycling Performance of Ni-Rich Positive Electrodes (NMC) in Li-Ion Batteries by Reducing Electrolyte Free-Solvent Activity Tatara, Ryoichi; Yu, Yang; Karayaylali, Pinar ACS Applied Materials & Interfaces, Vol. 11, Issue 38 https://doi.org/10.1021/acsami.9b11942	journal	June 2019
Structural and Electrochemical Aspects of LiNi _0.8 Co _0.1 Mn _0.1 O ₂ Cathode Materials Doped by Various Cations Weigel, Tina; Schipper, Florian; Erickson, Evan M. ACS Energy Letters, Vol. 4, Issue 2 https://doi.org/10.1021/acsenergylett.8b02302	journal	January 2019
Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe ₂ O ₃ –FeF ₃ Conversion Compounds by Direct Fluorination Zhou, Hui; Ruther, Rose E.; Adcock, Jamie ACS Nano, Vol. 9, Issue 3 https://doi.org/10.1021/acsnano.5b00191	journal	February 2015
Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery Fulvio, Pasquale F.; Brown, Suree S.; Adcock, Jamie Chemistry of Materials, Vol. 23, Issue 20 https://doi.org/10.1021/cm2012395	journal	October 2011
Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
Formation of Iron Oxyfluoride Phase on the Surface of Nano-Fe ₃ O ₄ Conversion Compound for Electrochemical Energy Storage Zhou, Hui; Nanda, Jagjit; Martha, Surendra K. The Journal of Physical Chemistry Letters, Vol. 4, Issue 21 https://doi.org/10.1021/jz402017h	journal	October 2013
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
High-energy cathode material for long-life and safe lithium batteries Sun, Yang-Kook; Myung, Seung-Taek; Park, Byung-Chun Nature Materials, Vol. 8, Issue 4 https://doi.org/10.1038/nmat2418	journal	March 2009
Reviving the lithium metal anode for high-energy batteries Lin, Dingchang; Liu, Yayuan; Cui, Yi Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2017.16	journal	March 2017
High energy-density and reversibility of iron fluoride cathode enabled via an intercalation-extrusion reaction Fan, Xiulin; Hu, Enyuan; Ji, Xiao Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04476-2	journal	June 2018
All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents Fan, Xiulin; Ji, Xiao; Chen, Long Nature Energy, Vol. 4, Issue 10 https://doi.org/10.1038/s41560-019-0474-3	journal	October 2019
Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte Xue, Weijiang; Huang, Mingjun; Li, Yutao Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00792-y	journal	March 2021
Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries Fan, Xiulin; Chen, Long; Borodin, Oleg Nature Nanotechnology, Vol. 13, Issue 8 https://doi.org/10.1038/s41565-018-0183-2	journal	July 2018
Self-smoothing anode for achieving high-energy lithium metal batteries under realistic conditions Niu, Chaojiang; Pan, Huilin; Xu, Wu Nature Nanotechnology, Vol. 14, Issue 6 https://doi.org/10.1038/s41565-019-0427-9	journal	April 2019
Role of precursor chemistry in the direct fluorination to form titanium based conversion anodes for lithium ion batteries Powell, Jonathan M.; Adcock, Jamie; Dai, Sheng RSC Advances, Vol. 5, Issue 108 https://doi.org/10.1039/C5RA17258F	journal	January 2015
Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox House, Robert A.; Jin, Liyu; Maitra, Urmimala Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C7EE03195E	journal	January 2018
Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering Jafta, Charl J.; Sun, Xiao-Guang; Veith, Gabriel M. Energy & Environmental Science, Vol. 12, Issue 6 https://doi.org/10.1039/C8EE02703J	journal	January 2019
Selective electrochemical fluorination of organic molecules and macromolecules in ionic liquids Fuchigami, Toshio; Inagi, Shinsuke Chemical Communications, Vol. 47, Issue 37 https://doi.org/10.1039/c1cc12414e	journal	January 2011
Towards the selective modification of soft-templated mesoporous carbon materials by elemental fluorine for energy storage devices Adcock, Jamie L.; Fulvio, Pasquale F.; Dai, Sheng Journal of Materials Chemistry A, Vol. 1, Issue 33 https://doi.org/10.1039/c3ta10700k	journal	January 2013
Factors that affect Li mobility in layered lithium transition metal oxides Kang, Kisuk; Ceder, Gerbrand Physical Review B, Vol. 74, Issue 9 https://doi.org/10.1103/PhysRevB.74.094105	journal	September 2006
Iron Oxyfluorides as High Capacity Cathode Materials for Lithium Batteries Pereira, N.; Badway, F.; Wartelsky, M. Journal of The Electrochemical Society, Vol. 156, Issue 6, p. A407-A416 https://doi.org/10.1149/1.3106132	journal	January 2009
Effect of Ambient Storage on the Degradation of Ni-Rich Positive Electrode Materials (NMC811) for Li-Ion Batteries Jung, Roland; Morasch, Robert; Karayaylali, Pinar Journal of The Electrochemical Society, Vol. 165, Issue 2 https://doi.org/10.1149/2.0401802jes	journal	January 2018

Similar Records

In Situ Ion‐Exchange Metathesis Induced Conformal LiF Surface Films on Cathode (NMC811) as a Cathode Electrolyte Interphase

Journal Article · 2023 · Advanced Functional Materials · OSTI ID:1997741

Thapaliya, Bishnu P.; Wang, Tao; Borisevich, Albina Y.; +5 more

Conformal LiF Stabilized Interfaces via Electrochemical Fluorination on High Voltage Spinel Cathodes (≈4.9 V) for Lithium-Ion Batteries

Journal Article · 2022 · Advanced Materials Interfaces · OSTI ID:1908083

Thapaliya, Bishnu Prasad; Borisevich, Albina Y.; Meyer III, Harry M.; +3 more

Enhanced cycling stability of Ni-rich Li-metal cells enabled by dual vinylene carbonate and tris(trimethylsilyl)borate electrolyte additives

Journal Article · 2026 · RSC Applied Interfaces · OSTI ID:3020264

Zhao, Zishuo; Lu, Yunyuan; Zhu, Yuwei; +3 more

Related Subjects

25 ENERGY STORAGE
conformal LiF
electrochemical fluorination
electromaterial functionalization
high energy density batteries
high-capacity cathodes

Title: Enhancing Cycling Stability and Capacity Retention of NMC811 Cathodes by Reengineering Interfaces via Electrochemical Fluorination

Citation Formats

References (46)

Similar Records

Related Subjects